CN100503436C - Carbon dioxide refining method - Google Patents
Carbon dioxide refining method Download PDFInfo
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- CN100503436C CN100503436C CNB200610087298XA CN200610087298A CN100503436C CN 100503436 C CN100503436 C CN 100503436C CN B200610087298X A CNB200610087298X A CN B200610087298XA CN 200610087298 A CN200610087298 A CN 200610087298A CN 100503436 C CN100503436 C CN 100503436C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Carbon And Carbon Compounds (AREA)
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Abstract
The invention relates to a method for producing carbon dioxide, which can restrain the steam generated by abundant oxygen and produce carbon dioxide effectively, when processing the oxidization reaction of carbon monoxide and nitrogen oxide in reaction tower. Wherein, said method comprises: guiding the mixed gas whose main component is carbon dioxide into reaction tower 16, as well as removing the nitrogen oxide of mixed gas via the reduction reaction with hydrogen gas, and removing the carbon monoxide gas via the oxidization reaction with oxygen gas; and the reaction condition is set as the outlet gas of reaction tower guided outside the reaction tower has non-reacted oxygen gas.
Description
Technical field
The present invention is about refining (refine) method of a kind of carbonic acid gas; Specifically, about a kind of recovery oil, natural gas liquids burning and gas-exhaustings such as (LNG), and remove the trace impurity that contained in the carbonic acid gas as its principal constituent method with refining carbonic acid gas; Especially about the pre-refining operation in a kind of operation of refining carbonic acid gas.
Background technology
Be used to obtain the method for carbonic acid gas, known have burning and gas-exhaustings such as the oil of recovery, Sweet natural gas, and various impurity are removed in this exhaust and the method for refining carbonic acid gas.Impurities in the burning and gas-exhausting that reclaims, the difference of based on fuel kind, combustion conditions etc. has than big-difference, mainly is nitrogen, oxygen, carbon monoxide, oxynitride (NO, NO
2Deng), sulfide (SOx, H
2S).In order to make the goods carbonic acid gas, must remove these impurity, especially, then must strictly limit the impurity concentration of being allowed in order to make food interpolation carbonic acid gas.
Making with extra care of carbonic acid gas generally is with absorption, absorption, reduction reaction, and perhaps each operation that causes decomposing because of oxidizing reaction is made up, and carries out pre-refining, then through liquefaction operation, distillation process.The combination of each operation in the pre-refining has various combinations, can be according to as conditions such as the temperature of the burning and gas-exhausting of raw material, pressure, and perhaps the composition of impurities is selected its best of breed.
In the above-mentioned various impurity, the dew point of its dew point and carbonic acid gas has the composition than big-difference, can more easily separate and remove by liquefying operation or distillation process.But, nitrogen peroxide (NO
2) can sneak into the character in the carbon dioxide liquid when having liquefied carbon dioxide, therefore must before distillation process, remove nitrogen peroxide fully.Specifically, generally be to remove NO by absorption or as the hydrogenation reduction of following formula
2
2NO
2+4H
2→N
2+4H
2O
Again, carbon monoxide can but then become paralyser (catalyst poison) with its separation in the liquefaction operation in above-mentioned reduction reaction, therefore preferably by represented oxidizing reaction in the following formula for example it is removed in advance.
2CO+O
2→2CO
2
For example, combustion exhaust (combustion gas) as rotation in future furnace gases boiler is the process for purification of the carbonic acid gas of raw material, following method is now proposed: adopt the pressure variation absorption method that carbonic acid gas is concentrated, and be forced into specified pressure, in thionizer, remove sulfide, condition with 60～100 ℃ of temperature, the about 300～500kPa of pressure (weather gauge pressure) imports it in hydrogenation decomposition tower then, with oxygen and decompose nitrogen oxides is nitrogen and water, further moisture is removed with moisture eliminator in the pressurization back then, and removes remaining micro-SO in the deodorization tower
2, H
2S, NO
2Deng, obtain highly purified carbonic acid gas (for example, with reference to Japanese patent laid-open 5-124808 communique) with the liquefaction water distilling apparatus at last.
Again, when utilizing hydrogenation reduction when removing the impurity in the carbonic acid gas, for the influence of the paralyser avoiding causing, can adopt and only remove carbon monoxide in advance, perhaps the method for utilizing superfluous oxygen simultaneous oxidation to remove carbon monoxide by contained carbon monoxide.Following method is for example now proposed: in order to avoid the influence of the paralyser that carbon monoxide causes, then in advance in the presence of oxygen oxidation remove carbon monoxide, oxynitride (for example, with reference to Japanese patent laid-open 4-219309 communique) is removed in reduction in the presence of hydrogen then.At this moment the reaction conditions of oxidizing carbon monoxide is: catalyzer is to use platinum or palladium, and temperature is set at 100～200 ℃, in the reduction reaction of the oxynitride in the presence of hydrogen, temperature is made as 40～100 ℃ then.
The speed of response of known oxygen and reducing gas, faster than other speed of response usually, therefore it is generally acknowledged to be reduced then by oxygen earlier oxynitride is reduced (for example, opening clear 51-87470 communique with reference to the Japanese Patent spy) again.Therefore, remove at the same time in the method for oxynitride and carbon monoxide, previous, except that the hydrogen that nitrogen oxides reduction is used, also must supply with to be used for reducing fully and be used for oxidizing carbon monoxide and the hydrogen of the oxygen of excessive interpolation.For example, when in feed carbon dioxide, containing the oxygen of 200ppm and the nitrogen protoxide of 100ppm (NO), if under 100～120 ℃ of temperature simultaneously with its reduction, the hydrogen that then is respectively applied for reduction and is consumed is respectively 400ppm and 100ppm (for example, with reference to Japanese patent laid-open 2-43923 communique).That is,, reduce the needed hydrogen of oxygen of excessive existence sometimes according to the composition of feed carbon dioxide, also many as the needed hydrogen of oxynitride of removing object than reduction.
Summary of the invention
In the method for removing carbon monoxide in advance, can distinguish the top condition of selective oxidation reaction, reduction reaction, but increasing reaction tower not only increases prime cost (initial cost), area is set, and safeguard also increase.If consider these factors, then preferred its constitutes the method that machinery is less and can remove oxynitride and carbon monoxide simultaneously.
But, remove at the same time in the method for oxynitride and carbon monoxide, also produce sometimes and reduce the required hydrogen of excessive oxygen as mentioned above than the more situation of the required hydrogen of nitrogen oxides reduction, thereby the problem that exists running cost (running cost) to increase.
Herein, in order at high temperature to carry out the reduction reaction of oxynitride, if consider thermo-efficiency, then preferably in the front and back of reaction tower interchanger being set carries out energy recovery.But should be taken into account following problem: in the reduction reaction of oxynitride and oxygen, have water vapor to generate, so the result of reduction excess of oxygen is: if produce a large amount of water vapors, then can be in interchanger condensing and perishable interchanger.In a word, should be contemplated to following problem: when using aluminum plate shell heat exchanger (plate-fin heat exchanger), because of corrosion causes stream perforation etc.
Therefore, the object of the present invention is to provide a kind of process for purification of carbonic acid gas, even when wherein in reaction tower, carrying out the reduction reaction of the oxidizing reaction of carbon monoxide and oxynitride simultaneously, also can suppress to reduce the water vapor that excessive oxygen produced as much as possible, simultaneously pre-refining carbonic acid gas efficiently.
For achieving the above object, the process for purification of carbonic acid gas of the present invention, be to be that the mixed gas of carbonic acid gas imports in the reaction tower with principal constituent, remove oxynitride in this mixed gas by carrying out reduction reaction, simultaneously by carrying out the process for purification that oxidizing reaction is removed the carbonic acid gas of carbon monoxide with oxygen with hydrogen; It is characterized in that, the reaction conditions in the above-mentioned reaction tower is set at: remaining unreacted oxygen the reaction tower exit gas of deriving from reaction tower outlet place; Amounts of hydrogen in the mixed gas of above-mentioned reaction tower ingress is set at, less than the required normal amount of oxygen in this mixed gas of reduction.
And then the process for purification of carbonic acid gas of the present invention is characterized in that: the temperature of reaction in the above-mentioned reaction tower is set at smaller or equal to 110 ℃; In addition, amounts of hydrogen in the mixed gas of above-mentioned reaction tower ingress is set at following amount: the above-mentioned mixed gas and the above-mentioned reaction tower exit gas that will import in this reaction tower carry out heat exchange, then above-mentioned mixed gas is heated up, with the cooling of above-mentioned reaction tower exit gas, the water vapor pressure the reaction tower exit gas after the cooling that this interchanger is derived is less than saturated vapor pressure simultaneously; And it is characterized in that: above-mentioned oxygen autoreaction system is added into outward in the above-mentioned mixed gas.
In the process for purification of carbonic acid gas of the present invention, must through reduction reaction with feed carbon dioxide in institute's nitrogen-containing oxide remove, and have carbon monoxide in the carbonic acid gas as object; When needing excessive oxygen, directly from reaction tower, discharge, then can reduce the feed rate of the refining required hydrogen of carbonic acid gas by making part of oxygen not add reaction for its influence as paralyser is controlled at inferior limit.This is by supplying with the equivalent hydrogen still less than the reduction reaction of oxygen, and temperature of reaction is made as 110 ℃ the temperature of being lower than as general catalyzed reaction, and the control effect that oxygen reduction produced.And, can remove carbon monoxide, oxynitride simultaneously with a reaction tower, especially contained carbon monoxide and oxygen concentration are than under the condition with higher in feed carbon dioxide, and it is apparent that effect of the present invention becomes.
And then, because the amount of oxygen that is reduced is less, so the quantity of steam that is generated is less, the therefore less worry corrosion of equipment in the operation afterwards, and can reduce the needed loading capacity of water adsorption device.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
Description of drawings
Fig. 1 is the system diagram of an example of the expression refining plant that uses CO 2 refining method of the present invention.
Fig. 2 (A), 2 (B), 2 (C) are the explanatory views of the structure example of expression reaction tower.
11: compressor 12: the deodorization tower
13: drying tower 14: interchanger
15: well heater 16,16a, 16b: reaction tower
17: dehumidification tower 18: the co 2 liquefaction device
19,50,51,52: pipe arrangement A, B: catalyst layer
Embodiment
Fig. 1 is the system diagram of an example of the refining plant that uses of expression CO 2 refining method of the present invention.
At first, will be from being after high-temp combustion exhaust in the generating set etc. of raw material is cooled off, to implement processing such as dedusting with oil, natural gas liquids (LNG), with compressor 11 it is forced into the pressure of setting after making unstripped gas.The principal constituent of this unstripped gas is a carbonic acid gas, wherein contains micro-carbon monoxide, nitrogen protoxide, nitrogen peroxide, oxygen, hydrogen, hydrogen sulfide, oxysulfide, water vapor etc.
In addition, when in the unstripped gas when oxygen-free gas, hydrogen, also can outside reaction system, suitably add oxygen, hydrogen by pipe arrangement 50,51.When supplying with oxygen, also can replace oxygen by air supply.In addition, when from pipe arrangement 50, adding hydrogen, its concentration is set at less than reducing the needed normal density of hydrogen of oxygen that mixes existence fully.
The unstripped gas of pressurization is imported in deodorization tower 12, the drying tower 13, to remove sulphur compound contained in the unstripped gas, water vapor etc.Then, with interchanger 14, well heater 15 unstripped gas is warming up to the temperature of setting.Afterwards, the exhaust that has heated up is imported in the reaction tower 16.
Contain the catalyst layer of removing carbon monoxide and oxynitride simultaneously in the reaction tower 16.Catalyst layer in the reaction tower 16 can the represented mode of Fig. 2 (A), catalyst filling layer A, the catalyzer that B is different; Also can be as the represented mode of Fig. 2 (B), be divided into two sections and fill identical catalyst layer A.In addition, also can reaction tower be divided into two tower 16a, 16b as the represented mode of Fig. 2 (C).Filling under the situation of different catalysts, even in a catalyst layer, also can remove carbon monoxide and oxynitride in the carbonic acid gas simultaneously.
In reaction tower 16, by removing oxynitride in this unstripped gas with the reduction reaction of hydrogen, simultaneously when removing carbon monoxide with the oxidizing reaction of oxygen, the reaction conditionss in the reaction tower 16 are set at remainingly the reaction tower exit gas of being derived from the reaction tower outlet has unreacted oxygen; By being filled in inner catalyzer, remove carbon monoxide and nitrogen protoxide by oxidizing reaction and reduction reaction respectively.At this moment, carry out oxidizing reaction and reduction reaction simultaneously, temperature of reaction is controlled at smaller or equal to 110 ℃, preferred 90～100 ℃ with a catalyst layer.
Can be reduced to less than and reduce the concentration of required normal hydrogen fully by mixing the oxygen concentration that exists, and temperature of reaction is controlled at smaller or equal to 110 ℃, and the reduction reaction (O of control oxygen
2+ 2H
2→ 2H
2And reduce the reduction hydrogen that oxygen consumed O).By the reduction reaction of inhibition oxygen, and unreacted oxygen is derived from reaction tower 16.
Reclaim the heat energy in the unstripped gas (gas in reaction tower exit) that contains nitrogen, oxygen, hydrogen, water vapor etc. with interchanger 14.At this moment, amounts of hydrogen in the unstripped gas of above-mentioned reaction tower 16 ingress is set at, be less than the amount of the oxygen aequum in this unstripped gas of reduction, and suppress the reduction reaction of oxygen, so the vapour content of being derived in the unstripped gas in the autoreaction tower 16 also tails off.Therefore, even in interchanger 14, the temperature of unstripped gas is reduced, also have the condensing phenomenon that produces water vapor hardly.
The unstripped gas that to discharge in interchanger 14 imports in the dehumidification tower 17 that is used alternatingly, and materials such as water vapor are removed in absorption.To import from the unstripped gas that contains nitrogen, oxygen, hydrogen that dehumidification tower 17 is derived the co 2 liquefaction device 18, in pipe arrangement 19, obtain goods liquefied carbon dioxides (LCO) by the liquefaction distillation.Dehumidification tower 17 can be common employed dehumidifying device, for example can use the adsorber of filling zeolite etc.
Nitrogen, oxygen, the hydrogen of trace are discharged to from co 2 liquefaction device 18 in the Purge gas (purge gas) of pipe arrangement 52.According to condition, again it is imported in the unstripped gas by reclaiming clean gas, the oxygen in the Purge gas, hydrogen can be utilized again.
[embodiment 1]
Use a reaction tower of having filled platinum group catalyst,, remove carbon monoxide and nitric oxide production test simultaneously containing micro CO and nitric oxide production feed carbon dioxide gas.Oxygen concentration in the feed carbon dioxide is made as about 150～300ppm.Reduction oxygen required density of hydrogen is made as about 300～600ppm, but in order to suppress the reduction reaction of oxygen, and the density of hydrogen of reaction tower ingress is set at 50～100ppm.Test is to carry out in the scope of 90～110 ℃ of temperature, pressure 600～900kPa (absolute pressure).It the results are shown in table 1.
[table 1]
-: analyze below the boundary
In the method formerly, as mentioned above, be in the reaction of purpose with the nitrogen oxides reduction, using 40～120 ℃ temperature of reaction; In addition, remove at the same time in carbon monoxide and the nitric oxide production reaction, use 100～200 ℃ temperature of reaction.
Generally speaking, temperature is high more to promote reaction more, if still temperature of reaction then also might produce ammonia (NH above 120 ℃
3).Confirm, under any circumstance all can remove carbon monoxide and nitrogen protoxide simultaneously, and do not producing ammonia below 110 ℃.It is generally acknowledged, in the feed carbon dioxide oxygenous about 10～20% by hydrogen reducing, but remaining about 80～90% unreacteds, this can obtain in the reaction tower exit to confirm.That is, be set at smaller or equal to the required normal density of hydrogen of reduction oxygen by the density of hydrogen with the reaction tower ingress, can suppress the reduction of oxygen, the required amounts of hydrogen of the oxygen of in other words can confirming to reduce reduces.In addition, 80～90% oxygen unreacted is arranged approximately, this also suppresses the generation of water vapor.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the structure that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, but every content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (3)
1. the process for purification of a carbonic acid gas, it is characterized in that: be in the mixed gas importing reaction tower of carbonic acid gas with principal constituent, the reduction reaction of utilization and hydrogen is removed the oxynitride in this mixed gas simultaneously, and the oxidizing reaction of utilization and oxygen is removed carbon monoxide;
Reaction conditions in the above-mentioned reaction tower is set at, unreacted oxygen is arranged remaining from the reaction tower exit gas that reaction tower outlet is derived;
Amounts of hydrogen in the mixed gas of above-mentioned reaction tower ingress is set at, less than the required normal amount of oxygen in this mixed gas of reduction;
Temperature of reaction in the above-mentioned reaction tower is set at smaller or equal to 110 ℃.
2. the process for purification of carbonic acid gas according to claim 1, it is characterized in that: the amounts of hydrogen in the mixed gas of above-mentioned reaction tower ingress is set at following amount: in interchanger, make the above-mentioned mixed gas that imports in this reaction tower and the gas in above-mentioned reaction tower exit carry out heat exchange, so that above-mentioned mixed gas heats up, make the gas cooling in above-mentioned reaction tower exit simultaneously, the water vapour pressure from the reaction tower exit gas after the cooling that this interchanger is derived is less than the pressure of saturated vapor.
3. the process for purification of carbonic acid gas according to claim 1 is characterized in that: above-mentioned oxygen autoreaction system is added into outward in the above-mentioned mixed gas.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005176353 | 2005-06-16 | ||
| JP2005176353 | 2005-06-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1880219A CN1880219A (en) | 2006-12-20 |
| CN100503436C true CN100503436C (en) | 2009-06-24 |
Family
ID=37518615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610087298XA Expired - Fee Related CN100503436C (en) | 2005-06-16 | 2006-06-14 | Carbon dioxide refining method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4382770B2 (en) |
| KR (1) | KR100751167B1 (en) |
| CN (1) | CN100503436C (en) |
| TW (1) | TWI330168B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4922010B2 (en) * | 2007-02-22 | 2012-04-25 | 大阪瓦斯株式会社 | CO2 supply device for plant growth using exhaust gas |
| JP5059063B2 (en) * | 2009-07-14 | 2012-10-24 | 公益財団法人地球環境産業技術研究機構 | Method for removing impurities in carbon dioxide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ID22518A (en) * | 1998-04-24 | 1999-10-28 | Praxair Technology Inc | CO2 PURIFICATION SYSTEM |
| JP2005506694A (en) * | 2001-10-17 | 2005-03-03 | プラクスエア・テクノロジー・インコーポレイテッド | Central carbon dioxide purifier |
-
2006
- 2006-05-30 JP JP2006149112A patent/JP4382770B2/en active Active
- 2006-06-07 TW TW095120178A patent/TWI330168B/en not_active IP Right Cessation
- 2006-06-14 KR KR1020060053447A patent/KR100751167B1/en not_active IP Right Cessation
- 2006-06-14 CN CNB200610087298XA patent/CN100503436C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007022906A (en) | 2007-02-01 |
| TWI330168B (en) | 2010-09-11 |
| CN1880219A (en) | 2006-12-20 |
| TW200700315A (en) | 2007-01-01 |
| KR100751167B1 (en) | 2007-08-22 |
| KR20060131648A (en) | 2006-12-20 |
| JP4382770B2 (en) | 2009-12-16 |
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